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J . A m . Chem. SOC.1991, 113, 3188-3189
complex 6 was isolated from preparative-scale reactions between equimolar amounts of reactants at 20 OC. It is intensely soluble in hexane (ca. 1 g/mL), from which it can be crystallized at -80 OC. Tellurolysis of the remaining methyl group with a second equivalent of the tellurol is slow at room temperature, but on warming to 50 OC for 3 h, the maroon bis-tellurolate 7 is produced in high yield. We are now probing the reactivity of these compounds and attempting to extend the tellurolysis approach to a wider variety of main-group and transition-metal tellurolates.
Acknowledgment is made to the donors of the Petroleum Research Fund, administered by the American Chemical Society, for partial support of this work and the Department of Education for a fellowship (to P.J.B.). Supplementary Material Available: Spectroscopic and analytical data for new compounds (1 page). Ordering information is given on any current masthead page.
Synthesis and Crystal Structure of a Spherical Polyoxovanadium Organophosphonate Anion: [Hl*(VO*),*(C6H5P03)81C G. Huan,*-la V. W. Day,Ib A. J. Jacobson,la and D. P. Goshomla Exxon Research & Engineering Company Annandale, New Jersey 08801 Crystalytics Company, Lincoln, Nebraska 68501 Received December 10, 1990 Several polyoxovanadates have recently been shown to form inclusion compounds with neutral molecules, for example, [V12036(CH3CN)l~,~ [V1~042(H20)1~~-9~ [As6V1s042(H20)1~,~ and [ A S ~ V ~ ~ O ~ ~ ( O . ~and H ~with O ) ] anions ~ - , ~ in [H9V18042(Vo4)lb, [Vl~042(S04)18-,[H4V18042(X)1+(X = C1, Br, I), and [vl&(Y)]b (Y = CI, Br, C03).6-8 In one case, [V12036(CH3CN)]e,2 the inclusion process is reversible, and consequently this compound can be considered a molecular analogue of the microporous oxides. Very recently, a vanadium organophosphonate anion, [H6(V02)16(CH3P03)8]8-, which includes a tetramethylammonium cation, has been reportedG9 In this communication, the synthesis and structure of a new vanadium organophmphonate, [N(C3H7)414[H12(V02)I2(C6HS~3)8l'l.48H20 (I), containing a large spherical anion, {VI2P8048),analogous to the {Vl8O42)systems is described. Blue, parallelepiped crystals of 1 were prepared in -70% yield by hydrothermal reaction of C6H5PO3H2(0.952 g), VOS04-3H20 (0.434 g), and tetra-n-propylammonium hydroxide (8.2 g, 1 M in H 2 0 ) at 200 OC for 2 days.I0 ( I ) (a) Exxon Research & Engineering Company. (b) Crystalytics Company. (2) Day, V. W.; Klemperer, W.G.; Yaghi, 0. M. J. Am. Chem. Soc. 1989, 111,5959. (3) Johnson, G.K.; Schlemper, E. 0.J. Am. Chem. Soc. 1978,100,3645. (4) Miiller, A.; DBring, J. Angew. Chem. 1988, 100, 1789; Angew. Chem., Int. Ed. Engl. 1988, 27, 1721. (5) Huan, G.; Greaney, M. A.; Jacobson, A. J. J . Chem. Soc., Chem
Commun., in press. (6) Miiller, A.; DBring, J.; BBgge, H.; Krickmeyer, E. Chimia 1988, 42, 300. (7) Miiller, A.; Krickemeyer, E.; Penk, M.; Walberg, H.-J.; BBgge, H. Angew. Chem. 1987,99, 1060; Angew. Chem., Int. Ed. Engl. 1987,26, 1045. (8) Miiller, A.; Penk, M.; Rohfling, R.; Krickmeyer, E.; DBring, J. Angew. Chem. 1990. 102. 927; Angew. Chem., Int. Ed. Engl. 1990, 29, 926. (9) Huan, G.; Jacobson, A. J.; Day, V. W. Angew Chem., in press.
0002-7863/91/1513-3188$02.50/0
X-ray structural analysis'] of 1 revealed the presence of discrete TPA' (tetra-n-propylammonium) cations and disordered water molecules of crystallization in the lattice and inside the two crystallographically independent [HI2(VO2)12(C6HSP03)8]e anions per asymmetric unit (Figure 1). Each anion possesses rigorous crystallographic Ci-7 symmetry and consists of six condensed vanadium-oxygen dimers covalently connected by eight P 0 3 C tetrahedra through corner-sharing oxygen atoms. Vanadium atoms are square-pyramidally coordinated by one doubly bonded terminal oxygen atom, two doubly bridging V-(OH)-V hydroxyl oxygens, and two doubly bridging V-0-P oxygen atoms. Each VOs unit shares one of its edges to form an 02-VO-(OH)2-V0-02dimer, and each C6H5PO3unit is bonded to three vanadium oxygen dimers. The protons of each dimer are positioned favorably to form hydrogen bonds which stabilize the anion structure (Figure 1). The phenyl groups, as well as the terminal (vanadyl) oxygen atoms, protrude from the surface of the "ball" forming a hydrophobic shell. Disordered water molecules were found at four partial occupancy (0.13-0.15) sites inside each anion. Each of these water molecules (03w, 04w,OSw,and 06w) appears to be weakly coordinated to the vanadium atoms of a O2-V0-(OH)2-VO-02 dimer at bridging sites as shown in Figure 2. The V-0 distances and V U V angles for these water molecules have ranges of 2.85 (6)-3.37 ( 6 ) A and 57 (6)-60 (6)O, respectively, and the O=V-O(water) angles range from 162 (1)O to 178 (1)'. and Osw.-06w distances are 2.49 and 2.53 A, Since the 03w...04w respectively, and each water molecule has a V4(water)--O(water) angle in the range 102-123', the included water molecules may exist as hydrogen-bonded and weakly complexed pairs. The 12 vanadium and eight phosphorus atoms of each anion are located at the vertices of a pentagonal dodecahedron (Figure 2); each of its 12 faces is a distorted pentagon consisting of three vanadium atoms and two phosphorus atoms. The V-V and P-V separations have ranges of 3.082 (2)-3.106 (1) A and 3.295 (2)-3.352 ( I ) A, respectively. Magnetic susceptibility data of 1 measured from 7 to 300 K show a broad maximum at 50 K indicating antiferromagnetic exchange interactions between the dl V(IV) ions in the dimers. Similar behavior is observed for the layered compounds VO(HP04)0.5H20, (V0)2P20,, VOSe03H20,and VOSe03,12-1s which contain similar structural units. The [ H , ~ ( V O ~ ) ~ ~ ( C ~ H cage S P Ois~a)new S ] ~type of spherical anion structure which resembles the previously reported (V18O42) systems in having sufficient internal volume for the inclusion of (IO) Anal. Calcd for C,6H,6,N8V,,P804,,,: C, 38.08; H, 5.56; N, 1.85; V, 20.19; P, 8.18. Found: C, 37.81; H , 5.47; N , 1.80; V, 20.21; P, 8.52. 1 is only slightly soluble in water but dissolves in mineral acids. Redox titration of 1in sulfuric acid solution gave an average vanadium oxidation state of 4.00 f 0.02. IR (solid/KBr): Y (cm-I) 1130 (vs), 11 IO (vs), 1030 (vs), 1010 (vs), 990 (vs), 905 (s), 755 (m), 715 (s), 690 (s), 590 (m), 540 (s), 510 (s). ( I 1) 1: triclinic, space group P i (No. 2) with a = 16.038 (3) A, b = 16.782 (3) A, c = 29.345 (5) A, a = 86.04 (2)O, j3 = 82.45 (2)O, y = 63.41 (2)', V = 7002 (2) A), and Z = 2 (daw = 1.436 g cm"; pn(MoKa) = 0.90 mm-I). A total of 19255 independent reflections having 28 < 45.8O were collected on a Nicolet autodiffractometer using w scans and graphite-monochromated Mo K a radiation. The structure was solved by using SHELXTL-Plus direct method techniques, and the resulting structural parameters have been refined by using counterweighted block-diagonal least-squares techniques to R, (unweighted, based on F) = 0.053 and R2(weighted, based on F) = 0.066 for 11 988 independent reflections having 28 < 45.8O and I > 340). These refinement cycles employed anisotropic thermal parameters for all non-hydrogen atoms (except C4al-C4Mand 02.-06,, which were isotropically refined) and isotropic thermal parameters for all anion hydrogen atoms. Hydroxyl hydrogen atoms Hl,-Hl, and H,,-H,, on anions 1 and 2 were located from a difference Fourier map and refined as independent isotropic atoms. The remaining (phenyl) hydrogen atoms on the anions were fixed at idealized sp*-hybridized positions. (12) (a) Leonowicz, M. E.; Johnson, J. W.; Shannon, H. F., Jr.; Brody, J . F.; Newsam, J. M. J . Solid. Sfate Chem. 1985, 56, 370. (b) Torardi, C. C.; Calabrese, J. C. Inorg. Chem. 1984, 23, 1308. (13) Johnston, D. C.; Johnson, J. W.; Goshorn, D. P.; Jacobson, A. J. J . Phys. Rev. B 1987, 35, 219. (14) Huan, G.; Johnson, J . W.; Jacobson, A. J.; Goshorn, D. P.; Merola, J. S. Chem. Mater., in press. (1 5 ) (a) Trombe, J.-C.; Gleizes, A,; Galy, J. C.R. Seances Acad. Sci. Ser. I I 1983, 297, 667. (b) Trombe, J.-C.; Gleizes, A,; Galy, J.; Renard, J.-P.; Journaux, Y.; Verdaguer, M. Nouu. J . Chim. 1987, 11, 321.
0 1991 American Chemical Society
J. Am. Chem. SOC.1991, 113, 3189-3190
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Preparation of Molecular Sieves from Dense, Layered Metal Oxides M. E. Landis,* B. A. Aufdembrink, P. Chu, I. D. Johnson, G. W. Kirker, and M . K. Rubin Mobil Research and Development Corporation Paulsboro Research Laboratory, P.O. Box 480 Paulsboro. New Jersey 08066-0480 Received November 19, 1990 013
Figure 1. Perspective plot of one of the two crystallographically indein 1 with the phenyl groups pendent [ H 1 2 ( V 0 2 ) , 2 ( C 6 H s P 0 3 ) 8anions ]k omitted for clarity. Hydrogen bonds a r e represented by dashed lines. Atoms labeled with a prime are related to nonprimed atoms by the crystallographic inversion center. Bond distances (A) and angles (deg) of interest: V-V, 3.082 (2)-3.106 (1); V-O,,,,, 1.568 (6)-1.590 (7); V-(/L~-O(H)), 1.936 (6)-1.980 (6); V-(/LZ-O), 1.942 (5)-1.986 (4); Otcrm-V-(~(2-O(H)), 105.7 (2)-110.7 (2); 0ter,-V-(~2-0), 103.6 (2)-108.9 (3); (p2-0)-V-(~(2-0), 74.4 (2)-76.1 (2); (p2-0)-V-(p2-0( H ) ) , 89.5 (2)-92.4 (2) and 140.7 (2)-150.5 (2); (p2-0)-V-(p2-0(H)), 82.9 (2)-84.3 (2). 015'
016'
We now report a novel pillaring procedure to convert dense, layered metal oxides and silicates into high surface area molecular sieves with large interlayer separations. The procedure is applicable to a wide variety of layered phases and allows for the engineering of microporous materials with diverse compositions and physical properties. Over the past three decades, zeolite catalysis has had a dramatic impact upon petroleum refining and petrochemical processing.' Catalytic differences among zeolites are typically manifested by differences in product distributions as a consequence of unique zeolite channel or pore size and their framework aluminum content. To exploit the selectivity differences possible with different pore geometries and catalyst compositions, other classes of molecular sieves have been prepared which include aluminum phosphates (A1P04s)2*3and silica- and metal-modified AIP04s such as SAPOs4 and MeAP04s.5 Pillared or intercalated clays: layered phosphates,' and a layered tetratitanates are other classes of molecular sieves. Historically, these have been synthesized by incorporating cationic precursors to stable metal oxide pillars.6 The pore sizes of these pillared materials are determined by the size of the exchanging cation and are typically in the 8-9-A
The pillaring procedures developed for smectite clays are not generally applicable to the wide variety of laminar metal oxides that do not spontaneously delaminate in water. To tailor-make materials with varied but controllable pore sizes from metal oxides with unique chemistries, a new synthetic approach was created. We found that pillaring could be facilitated by utilizing a 013' preswelling step in which the interlayer is exposed to organo013 014' ammonium ions. According to procedures developed earlier, layered metal oxidesg and silicates'O were first intercalated with an aqueous solution of long-chain organoammonium salt or amine. An organic pillar precursor, such as tetraethyl orthosilicate (TEOS), was then absorbed into the organophilic interlayer region, where it was converted to a metal oxide pillar. Typically, the organoammonium ion exchanged product was stirred with excess TEOS for 1-3 days a t 25-80 OC,filtered, and dried. The final 015 microporous material was produced by calcination for several hours Figure 2. A drawing of the dodecahedral arrangement of the 12 vanain air at 538 "C, which removes the water, preswelling organodium and eight phosphorus atoms in the [ H , 2 ( V 0 2 ) i 2 ( C 6 H s P O ~ ) ~ ] ~ ammonium ion, and organic byproducts from TEOS hydrolysis, anion of Figure I . T h e terminally bonded oxygen on each vanadium is affording a silica-pillared product. Using this procedure, we have also shown as is one pair of included and weakly complexed water prepared porous products from a wide variety of layered oxides, and 04,J. molecules (03w including alkali titanates," alkali metal-substituted titanates water molecules during synthesis. However, the presence of additional atoms in the (V12Ps048J sphere results in a larger central (1) (a) Meisel, S. L.; McCullough, J. P.; Lechthaler, C. H.; Weisz, P. B. diameter and consequently a greater free volume. The average Chem. Technol. 1976, 86, 6. (b) Chen, N. Y.;Gorring, R. L.; Ireland, H. distance from the center of the sphere to an oxygen atom is 4.4 R.;Stein, T. R. Oil Gas J . 1977, 75, 165. A compared to the value of 3.675 A observed in [H4V18042(X)e (2) Wilson, S. T.; Lok, B. M.; Messina, C. A.; Cannan, T. R.;Flanigen, E. M. J. Am. Chem. Soc. 1982, 105, 1146. (X = Br, I), suggesting that the inclusion of still larger molecules (3) Davis, M. E.; Saldarriaga, C.; Montes, C.; Garces, J.; Crowder, C. or ions by the vanadium organophosphonate structure may be Narure 1988, 331, 698. possible. (4) Lok, B. M.; Messina, C. A.; Patton, R. L.; Gajek, R. T.; Cannan, T. R.;Flanigen, E. M. J . Am. Chem. SOC.1984, 106, 6092. Supplementary Material Available: Crystal structure analysis (5) Flanigen, E. M.; Lok, B. M.; Patton, R.L.; Wilson, S.T. Srud. Surf. Sei. Caral. 1986, 28. 103. report including Tables I-VI11 containing atomic coordinates for (6) (a) Pinnavaia, T. J. Science 1983, 220, 365. (b) Vaughan, D. E. W.; non-hydrogen atoms, anisotropic thermal parameters for nonLussier, R. J. In Proceedings of rhe 5th International Conference on Zeolites; hydrogen atoms, atomic coordinates for anion hydrogen atoms, Rees, L. V. C., Ed.; Hyden: London, 1980; p 94. (c) Vaughan, D. E. W. ACS bond lengths and angles for the anion and cation non-hydrogen Symp. Ser. 1988, 368, 308. (7) Clearfield, A.; Roberts, B. D. Znorg. Chem. 1988, 27, 3237. atoms, and close contacts involving hydrogen atoms for compound (8) Cheng, S.; Wang, T.-C. Inorg. Chem. 1989, 28, 1283. 1 (38 pages); table of observed and calculated structure factors (9) Weiss, A. Angew. Chem. 1960, 413. for compound 1 (43 pages). Ordering information is given on any (10) (a) Lagaly, G.; Beneke, K.; Weiss, A. Am. Mineral. 1975, 60, 650. current masthead page. (b) Beneke, K.; Legaly, G. Am. Mineral. 1983, 68, 818. 0002-7863191115 13-3189%02.50/0 0 1991 American Chemical Society
